Methods and Systems for Making Metal Hydride Slurries

ABSTRACT

A method for making a metal-hydride slurry includes adding metal to a liquid carrier to create a metal slurry and hydriding the metal in the metal slurry to create a metal-hydride slurry. In some embodiments, a metal hydride is added to the liquid carrier of the metal slurry prior to hydriding the metal. The metal can be magnesium and the metal hydride can be magnesium hydride.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of and claims priority toU.S. application Ser. No. 12/820,737, filed Jun. 22, 2010, which is acontinuation of and claims priority to U.S. application Ser. No.11/392,149, filed Mar. 29, 2006. The disclosures of these priorapplications are incorporated by reference in their entirety.

TECHNICAL FIELD

This document relates to systems and techniques for making metal-hydrideslurries, particularly magnesium hydride slurries.

BACKGROUND

Energy in the form of electricity can be stored in the form of hydrogen,for example, by applying the electricity to an electrolysis process todisassociate the hydrogen from oxygen in water. Energy in the form ofheat can also be stored in the form of hydrogen by using a thermalconversion process to dissociate the hydrogen from oxygen in water.

Hydrogen can be incorporated into a metal hydride. Later, the hydrogencan be released by mixing water with the metal hydride and used toprovide energy, for example, to a car. Magnesium and hydrogen can beconverted into magnesium hydride using temperatures of 500° C. or higherand pressures of 200 atmospheres or higher. Catalysts can reduce therequired temperatures and pressures.

SUMMARY

This document describes systems and techniques that may be used toproduce slurries of metal hydrides. For example, methods of producingmagnesium hydride slurries are disclosed. In general, a method ofproducing a metal-hydride slurry includes combining a metal with aliquid carrier to form a metal slurry and hydriding the metal while itis in the slurry. Hydriding the metal in the presence of the liquidcarrier is safer than hydriding a metal without the presence of theliquid carrier of the slurry. When metal particles are mixed with liquidcarrier, the metal particles can be protected from moisture or oxygen inthe air. This can reduce the hazards associated with magnesium powderhandling. Some metal hydride formers are very reactive, thus thepresence of the liquid carrier can make the handling of such metalparticles safer. Metal particles can further be made or reduced in sizein the presence of the liquid carrier.

Hydriding the metal while in the slurry can also be cheaper. Byhydriding the metal in the presence of the surrounding liquid carrier,the slurry can be stirred to improve the heat transfer rates from heatedmetal particles to the surrounding liquid carrier, which can make theprocess more efficient and thus cheaper. The use of pumps to transportthe slurry can also reduce costs due to the elimination of moreexpensive techniques for safely handling magnesium powder.

Additionally, in some cases, metal hydride can be added to the slurrybefore hydriding the metal to help catalyze the reaction of the metal toa metal hydride.

The details of one or more embodiments are set forth in the accompanyingdrawings and the description below. Other features and advantages willbe apparent from the description and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 is a flow chart showing an exemplary process for making magnesiumhydride slurry.

FIG. 2 is a schematic diagram of a metal hydride charging device.

FIG. 3 is a schematic diagram of a metal hydride discharging device.

DETAILED DESCRIPTION

Generally, systems and methods are provided for forming metal hydrideslurries and for storing energy in the metal hydride slurries. The metalhydride slurries described herein can include a hydrided metal or ahydrided metal alloy. The metal or metal alloy can be dehydrided andrehydrided in a reversible fashion, depending on the conditions (e.g.,heat and/or pressure) to which the slurries are subject.

Methods for making metal-hydride slurries provided herein can includeadding metal to a liquid carrier to create a metal slurry and hydridingthe metal in the metal slurry to create a metal-hydride slurry.Hydriding the metal in the presence of the liquid carrier can be saferthan hydriding a metal without the presence of the liquid carrier of theslurry. When metal particles are mixed with the liquid carrier (e.g.,mineral oil), the metal or metal alloy can be protected from moisture oroxygen in the air. Some metal hydride forming metals are very reactivewith oxygen or water, thus the presence of the liquid carrier that canprotect the particles from oxygen or water can make the handling of themetals (e.g., metal particles) safer. Metal particles can further bemade or reduced in size in the presence of the liquid carrier.

Hydriding the metal while in the slurry can also be cheaper. Byhydriding the metal in the presence of the surrounding liquid carrier,the slurry can be stirred to improve the heat transfer rates from heatedmetal particles to the surrounding liquid carrier, which can make theprocess more efficient and thus cheaper. The process will be able to usepumps rather than powder handing technologies to move the powdered metaland agitation can be supplied with the movement of the slurry in thehydrider. Pumps are generally cheaper than powder handling processes.The primary reason for lower costs when using a slurry approach are thereduced risks associated with the handling of slurry rather thanhandling powder that must be protected from air and water. Additionally,in some cases, metal hydride can be added to the slurry before hydridingthe metal to help catalyze the reaction of the metal to a metal hydride.

FIG. 1 depicts an exemplary process 100 for making a metal-hydrideslurry provided herein. A metal or metal alloy can be used as thehydride former in a method provided herein. The metal or metal alloy canbe in the form of particles. FIG. 1 depicts a step 110 of forming metalparticles and a step 120 of mixing the metal particles with liquidcarrier to make a metal slurry. The particles can be formed before,during, or after being placed in the liquid carrier. For example, themetal or metal alloy can be formed into particles in the presence ofliquid carrier by crushing the metal/liquid carrier mixture. In somecases, the reversible hydride former powder is first combined with amixture of the mineral oil (and optionally a dispersant), which is thenground (e.g., in a grinder or mill) to further reduce the size of theparticles. In some cases, the final particles are primarily from about 1microns to about 200 microns (e.g., from about 1 microns to about 100microns or from about 1 micron to about 50 microns) in size across theirsmallest dimension. In some cases, a metal or metal alloy can be castinto particles, crushed into particles, machined into particles, orcrushed into particles prior to being introduced into the liquidcarrier.

In some cases, a metal or a metal alloy is melted and sprayed into aliquid carrier to create particles of metal or metal alloy that arecooled by the liquid carrier. In this process, the metal is melted andthen pumped through a nozzle to form a spray of particles. In somecases, a gas is introduced in the sprayer to help with the atomization.The liquid atomized droplets of the metal can be sprayed into a vesselto protect the droplets from contact with air or moisture. In thevessel, jets of gas and/or oil can be sprayed across the atomized jet tocool the particles. The particles can then be captured by the oil andremoved from the cooling chamber. The spraying and cooling processes canbe performed in a hydrogen atmosphere or in an inert gas atmosphere.

The particles can have any suitable dimensions. In some cases, theparticles have an average diameter of between 0.1 micron and 200 microns(e.g., between 0.5 microns and 50 microns, between 0.75 microns and 30microns, between 0.1 and 1 microns, between 1 and 10 microns, between 10microns and 20 microns, between 20 microns and 30 microns, between 30microns and 40 microns, between 40 microns and 50 microns, between 50microns and 60 microns, between 60 microns and 70 microns, between 70microns and 80 microns, between 80 microns and 90 microns, between 90microns and 100 microns, between 100 and 150 microns, or between 150microns and 200 microns). In some cases, the particles have an averagediameter of less than 5 microns.

FIG. 1 further depicts a step 130 of converting the metal particles intoa metal hydride. The reaction, in a simple form, involves bringinggaseous hydrogen in contact with the metal or metal alloy. This reactioncan be represented as follows:

M+x/2H₂

-

MH_(x)

where M is the metal or metal alloy and X is the number of hydrogenatoms in the final metal hydride product. This reaction is sometimesdescribed as an adsorption process rather than a bonding process.

The metal slurry can be converted into a metal-hydride slurry in acharging device. A charging device can include a slurry-holding vesseland a heating device (e.g., heating coils, a heat exchanger, a heatingplug, and/or a counter flow heat exchanger) for heating the metal slurrytherein to the charging temperature. The charging device also includes ahydrogen gas inlet and optionally a pressure regulator for maintainingthe charging pressure within the vessel. As the charging reaction isexothermic, the charging device may include a heat removal apparatus(e.g., a heat pump or a heat exchanger) for maintaining the slurry beingcharged within a desired temperature range. The charging device can alsoinclude stirring or mixing components to create a more uniformtemperature distribution throughout the slurry and to assist in thedistribution of hydrogen throughout the slurry. The charging device canbe supplied with freshly created metal slurry.

In some examples, the charging device operates on a batch-by-batchbasis. Metal slurry is pumped into the device, which is heated andsupplied with hydrogen gas until the metal slurry is converted into ametal-hydride slurry. The pressure is vented, the slurry is cooled, andthe metal-hydride slurry is pumped from the device (e.g., to a storagetank). The process is then repeated. In some cases, the charging deviceoperates continuously as slurry is continuously pumped, heated, charged,cooled and removed.

As shown in FIG. 2, in a continuous-mode charging apparatus 150, metalslurry 152 is fed by a pump 154 into a first section of tubing 156,where it is heated to the charging temperature by heating coils 158.Once heated, the metal slurry 152 is pumped into a pressure chamber 160having a headspace 161 located above the metal slurry 152. Hydrogen gas162 is introduced via gas inlets 163 into the headspace 161, where it isin direct contact with a surface 153 of the metal slurry 152. Thehydrogen gas 162 is introduced under pressure sufficient, given thetemperature selected, to initiate the hydride reaction. Alternatively,the hydrogen gas is introduced at the bottom of the slurry pool usingsparging tubes to produce many very small bubbles of hydrogen. Thehydrogen rising through the slurry increases the surface area of theslurry and promotes the rate of absorption by the metal hydride. Thepressure chamber 160 is of a length sufficient, when combined with theflow rate of the slurry, to result in a lag time of the slurry in thepressure chamber 160 sufficient for substantially complete charging ofthe slurry. As the metal in the metal slurry 152 is hydrided to form acharged metal-hydride slurry 168, heat is given off by the slurry. Anoptional heat exchanger 166 collects and transfers heat from the slurryto the first section of tubing 156, where it assists in the heating ofmetal slurry 152. Once the slurry is fully charged, it exits thepressure chamber 160 and enters a third section of tubing 172, in whichit is cooled to about room temperature, e.g., by the heat exchanger 166.The charged metal-hydride slurry is then pumped out of the chargingdevice 150.

In a variation of this arrangement, the process could be started bypumping some discharged metal-hydride slurry through a counter flow heatexchanger and then through a heater (that would raise the temperature ofthe discharged metal-hydride slurry to operating temperature) and theninto the charging volume where hydrogen will contact the slurry. Areaction between the metal or metal alloy and the hydrogen will produceheat, some of which must be removed actively to maintain the slurrytemperature at the desired reaction temperature. After being in thehydriding section for a couple hours, the hydriding should be completeand the charged metal-hydride slurry will pass back through the counterflow heat exchanger and into a separate container for the chargedmetal-hydride slurry. The hot slurry passing through one side of thecounter flow heat exchanger will lose its heat to the cold depletedslurry passing through the other side of the counter flow heatexchanger.

In some cases, the metal slurry can include some metal hydrides prior tobeing hydrided. The amount of metal hydride added to the metal slurry,in some embodiments, is from about 1% to about 50% (e.g., from about 3%to about 20%). For magnesium hydride, the hydride can function as acatalyst, increasing the rate of hydride formation by the reversiblehydride former, for example, as described in U.S. Pat. No. 5,198,207,which is hereby incorporated herein by reference. As used herein, theterm “metal slurry” is a slurry including virgin metal and optionallymetal hydride. Once the metal slurry is hydrided, it becomes a“metal-hydride slurry.” The presence of some amount of metal hydrides inthe metal slurry prior to hydriding the metal slurry to form themetal-hydride slurry can help catalyze the conversion of the metal orthe metal alloy into a metal hydride in the slurry. In some cases, themetal or metal alloy can be added to a liquid carrier that is in theform of a mixture of a liquid carrier and a metal hydride (e.g.,magnesium hydride). In some cases, the liquid carrier can include atleast 1.0 weight percent metal hydride prior to adding the metal ormetal alloy. In some cases, a small amount of metal hydride or a mixturecontaining metal hydride is added to the liquid carrier before or afteradding the metal or metal alloy to the liquid carrier to create a metalslurry including at least 1.0 weight percent metal hydride.

FIG. 1 depicts a recirculation in the process in order to include metalhydrides in the metal slurry. FIG. 1 depicts a process of splitting 132the resulting metal-hydride slurry and sending a side stream 134 ofmetal-hydride slurry to be mixed with the metal and/or metal alloy andthe liquid carrier to form the metal slurry. The split 132 can beconducted so that the metal slurry created in step 120 includes at least1.0 weight percent metal hydride (e.g., at least 1.2 weight percentmetal hydride, at least 3 weight percent metal hydride, or at least 5weight percent metal hydride) prior to hydriding the metal slurry. Theother stream 140 can then be used as a metal-hydride slurry in one ormore commercial operations.

In some cases, a metal slurry including metal hydrides can be createdusing multiple steps. For example, a metal or metal alloy can be addedto a liquid carrier to form a first metal slurry. The first metal slurrycan then be mixed with a metal-hydride slurry to form a second metalslurry that includes at least 1.2 weight percent metal hydride. Thesecond metal slurry can then be hydrided to form a metal-hydride slurry.A portion of that metal-hydride slurry can then be mixed with anotherstream or batch of metal slurry to again form a metal slurry thatincludes at least 1.0 weight percent metal hydride. For example, a firstmetal slurry (e.g., a slurry consisting essentially of liquid carrier(and optionally dispersants) and particles of virgin metal and/or virginmetal alloy) can be mixed with a metal-hydride slurry in a ratio of atleast 2:1 to form a second metal slurry.

Once the metal slurry is hydrided, the resulting metal-hydride slurry is“charged” or “partially charged.” Subsequent use of the metal-hydrideslurry, however, may release hydrogen and thus “deplete” or “partiallydeplete” the metal-hydride slurry. Metal-hydride slurries can generallybe described as “charged” when a substantial amount (e.g., 80% or more)of the hydridable component is hydrided; “depleted” when a substantialamount (e.g., 80% or more) of the hydridable component is not hydrided;or “partially charged”/“partially depleted” when the slurry containsboth hydrided and non-hydrided metal, with the hydrided metal beinggenerally present in an amount between about 20% and 80% of the totalamount of hydridable metal. In some cases, at least 70% of the metal inthe metal slurry is hydrided when the metal slurry is hydrided to becomethe metal-hydride slurry. In some cases, between 85% and 95% of thehydridable metal in the metal slurry will be hydrided during thehydriding of the metal slurry. In general, “charged” metal-hydrideslurries can include some level of hydridable component that is nothydrided, and a “depleted” metal-hydride slurry can include some levelof hydridable component that is hydrided.

The metal-hydride slurry provided herein can store energy from anyavailable source. In some cases, the metal-hydride slurry can be used totransport energy safely and efficiently. For example, energy availableat a first location (e.g., a windmill farm in Kansas) can be stored in ametal-hydride slurry provided herein and transported to a secondlocation (e.g., New York) where the energy can be used (e.g., in carsthat are able to burn hydrogen as a fuel). At a first location, wind cancause rotors of windmills to spin, driving generators to produceelectricity. The electricity can be carried on cables to electricalterminals of an electrolyzer. The system can also include a chargingdevice. Using the electricity, the electrolyzer can separate water intohydrogen gas and oxygen gas. The water can be provided from a sourcethrough a pipe. The hydrogen gas can be passed through a hydrogen gasoutlet and a pipe into the charging device. The oxygen gas can be ventedfrom the electrolyzer through an oxygen gas outlet, where it can becollected for further use or vented to the atmosphere. In some cases,the electrolyzer can pump the hydrogen gas into the charging deviceunder pressure (e.g., at least about 50 psia [pounds per square inchabsolute]) and the contents of the charging device can be maintainedunder pressure. The pressure can be in a range of about 100 psia ormore, 150 psia or more, 200 psia or more, 250 psia or more, 500 psia ormore, 1000 psia or more, or 1500 psia or more. The pressure level can beset based on the ability of the charging device to withstand pressureand handle the heat generated by the reaction. The reaction between themetal and the hydrogen can produce heat and charged metal hydride. Thereaction rate of the metal with hydrogen can be faster with higherpressure. In some cases, the slurry can be stirred to aid in heattransfer. In some cases, the walls of the charging device and/or thesurfaces of a stirrer can be coated with a catalyst that catalyzes theformation of metal hydrides. In some cases, the hydrogen gas can becollected in a hydrogen gas tank where it is pressurized before beingdelivered to a charging device. Additional details about how hydrogengas can be created, how a metal-hydride slurry can be hydrided, and howthe slurry can be transported can be found in columns 4 and 5 and FIG. 1of U.S. Pat. No. 7,790,013, which is hereby incorporated by reference inits entirety.

In some cases, a pressurized charging device can receive a stream ofmetal slurry provided herein and/or depleted metal-hydride slurry. Adepleted metal-hydride slurry can be a slurry that has been at leastpartially dehydrided. The proportion of metal hydride to elemental metalin the metal slurry or depleted metal-hydride slurry can be 1.0% or moreby weight.

The liquid carrier can be a liquid that does not chemically react eitherwith H₂ or with the metal hydride and/or metal or metal alloy at thetemperatures and pressure in which it will be used, and that will notdeactivate the surface of the hydride or metal or metal alloy inrelation to its catalytic capability to dissociate the H₂ molecule intoatoms or to prevent recombination of the atoms into the H₂ molecule. Theliquid carrier can have the capacity to dissolve measurable amounts ofhydrogen. The carrier liquid, in some cases, is an organic carrierliquid, such as mineral oil or a low molecular weight hydrocarbon, forexample, an alkane (e.g., pentane or hexane). In some case, the liquidcarrier is a light mineral oil. Other carrier liquids could includefluorinated hydrocarbons, such as perfluorodecane, silicone basedsolvents, saturated organic liquids, such as undecane, iso-octane,octane and cyclohexane, or mixtures of high boiling point hydrocarbonssuch as kerosene, and mixtures of them.

In some cases, the inert carrier liquid can be a non-toxic light mineraloil that exhibits a high flash point, in the range of about 154° C. toabout 177° C. and a viscosity in the range of about 42 Saybolt Universalseconds (S.U.s.) to about 59 S.U.s. The mineral oil is not chemicallyreactive with metal hydrides, produces relatively low vapor pressure,and remains liquid through a temperature range of about −40° C. to 200°C. The carrier liquid renders the metal-hydride slurry pumpable and, asa safe liquid, simple to store or transport. The carrier can act as abarrier between the hydride and atmospheric water, reducing the reactionof the two to form a hydroxide, which can reduce the ability of theslurry to store and release hydrogen. The use of a slurry permits easyrefueling, as by topping off a tank. Other carriers may work well,including carriers that are without water bonds and preferably arewithout OH bonds. Silicone-based carriers may also work for slurries.

In addition to the metal and/or the metal alloy, the metal hydride, andthe liquid carrier, other components can be included in the metalslurries provided herein. For example, a dispersant can be included forstabilizing the slurry. In some cases, the metal slurry and resultingmetal-hydride slurry can include a dispersant. The dispersant can be,for example, a triglyceride dispersant, which sterically stabilizes theslurry. The triglyceride dispersant can be, for example, triglyceride ofoleic acid, or triolein. Other dispersants that could be used includepolymeric dispersants, e.g., Hypermer™LP1. The dispersant can bepolymeric dispersant. A combination of triglyceride and polymericdispersant can also be used and may be particularly useful if thehydride is magnesium hydride. Other dispersants include oleic acid,polyacrylic acid, and hexadecyltrimethylammonium bromide (CTAB). Thedispersant can in some cases be present at concentrations in the metalslurry and/or the resulting metal-hydride slurry of at least about 0.05%(e.g., at least about 0.1%, at least about 0.5%, at least about 0.75%,at least about 1.0%, at least about 1.5%, at least about 2.0%, at leastabout 2.5%, at least about 3.0%, or at least about 3.5%) and/or at mostabout 4.0% (e.g., at most about 3.5%, at most about 3.0%, at most about2.5%, at most about 2.0%. at most about 1.5%, at most about 1.0%, atmost about 0.75%, at most about 0.5%, or at most about 0.1%). Forexample, a metal slurry can be hydrided to form a metal-hydride slurryincluding magnesium hydride, light mineral oil, and a mixture of 0.0625%CTAB with 1% poly(acrylic) acid forms a stable metal-hydride slurry.CTAB can make the slurry more flowable and the poly(acrylic) acid helpsto keep the magnesium hydride particles in suspension. The dispersantcan attach to the particles of hydride, increasing the drag of theparticle in the carrier fluid to thus help prevent settling. Thedispersant also helps to keep the particles from agglomerating. Thedispersant promotes the formation of the slurry and the stabilization ofthe hydride into the mineral oil. Dispersants can in certain embodimentsalso have surfactant properties that may also be useful in the formationof the slurry. For example, metal slurries provided herein can include atriglyceride or polyacrylic acid (−1%) or oleic acid (−0.125%) asdispersants. In some cases, the metal slurry can include hydridecatalyst. In some cases, the hydride catalyst is another metal (e.g.,vanadium, nickel, and/or iron).

The concentration of the metal in the metal slurry and the metal hydridein the charged metal-hydride slurry can be in the range of 40 to 80weight percent (e.g., 50 to 70 weight percent, or 55-60 weight percent).The use of denser metal hydrides can result in higher metal hydrideconcentrations than will the use of less dense metal hydrides. Densemetal hydrides are metal hydrides having a density of at least about 1gm/mL, and include, for example, lanthanum penta-nickel, while less 50dense metal hydrides have a density of no more than about 1 gm/mL, andinclude, for example, lithium hydride. Magnesium hydride slurries canhave hydride concentrations of at least about 50 weight percent (e.g.,at least about 55 weight percent, at least about 60 weight percent, atleast about 65 weight percent, at least about 70 weight percent, or atleast about 75 weight percent), and/or at most about 80 weight percent(e.g., at most about 75 weight percent, at most about 70 weight percent,at most about 65 weight percent, at most about 60 weight percent, or atmost about 55 weight percent). In some case, the metal slurry includesat least 50 weight percent magnesium and one or more elements selectedfrom the group consisting of vanadium, nickel, and iron.

In some cases, the metal and/or metal alloy in the metal slurry caninclude one or more of magnesium, vanadium, FeTi, LaNi₅, MgNi₂, NaAl orother metal hydride formers whether an elemental metal, metal alloy orintermetallic material. Intermetallic hydride formers includeLaNi₄₅AlO₅, LaNi₅ and TiFe₇Mn₂. Metallic hydride formers include thetransition metals (periodic table Groups IIIA to VIIIA), including thelanthanide and actinide series. They have a large capacity for hydrogenstorage coupled with ready release of hydrogen at moderate temperaturesand pressures and an ability to undergo many cycles of absorption anddesorption with little decrease in capacity. Metals and metal alloysknown to form reversible hydrides for reversibly capturing hydrogeninclude titanium alloys as set forth in U.S. Pat. No. 4,075,312,lanthanum alloys as disclosed in U.S. Pat. No. 4,142,300, and otheralloys as shown in U.S. Pat. No. 4,200,623. Elemental metals known toform metal hydrides are described in “Metal Hydrides” by W. M. Mueller,J. P. Blackledge and G. G. Libowitz, Academic Press, N.Y. 1968. Thesepatents and references are incorporated here by reference.

The metal slurries provided herein can be drawn by a pump through a pipefrom a metal slurry source and forced through a slurry inlet into thecharging device. The metal slurry in the pressurized charging device canthen be heated using heating coils. When the metal slurry is heated, themetal in the slurry can be further charged with hydrogen gas, wherebythe amount of hydrogen in the form of a metal hydride in the slurry isincreased to form a metal-hydride slurry. For magnesium hydride, thereaction rates are very slow until the temperature of the hydride isabove about 280° C., so heating the magnesium hydride to thistemperature can speed up the initial reaction. The rate then generallyquickens, and the temperature and/or pressure can be lowered to controlthe reaction rate. By this process, the metal slurry becomes a chargedmetal-hydride slurry. The temperature to which the pressurized slurry isheated for charging can be within a wide range, for example, in therange of from about 50° C. to about 350° C., depending on the metalhydride used in the slurry. For magnesium hydride, the charging range isfrom about 250° C. to about 400° C. (e.g., from about 260° C. to about300° C.).

After the charging, the metal-hydride slurry is cooled, e.g., to roomtemperature. The cooling of the metal-hydride slurry can happen beforeor after a side stream 134 is separated for recirculation for mixingwith another stream or batch of metal slurry. The cooled metal-hydrideslurry does not release a significant amount of hydrogen while itstemperature remains within a cool range, and is therefore safe to storeand/or transport. A “significant amount” of hydrogen is an amount largeenough to significantly affect the amount of energy available at thesite of hydrogen evolution or the cost-effectiveness of using the slurryas a source of energy, or enough to create storage and/or transportationdifficulties, for example, due to increases in pressure resulting fromthe production of hydrogen. For example, in some cases, the cooledcharged metal-hydride slurry releases no more than about 1% of its totalhydrogen (e.g., no more than about 10%, no more than about 1%, or nomore than about 0.1% of its total hydrogen). In some cases, the amountof hydrogen release can be less than 0.1%. The available range oftemperatures at which the charged metal-hydride slurry does not releasea significant amount of hydrogen depends on the metal hydride used inthe slurry. For magnesium hydride, the slurry will not producesignificant amounts of hydrogen at temperatures below about 200° C.(e.g., below about 100° C., below about 80° C., below about 60° C. orbelow about 40° C.). Other reversible hydrides may be kept cooler inorder to ensure that a significant amount of hydrogen is not released.In some cases, the metal-hydride slurry can be cooled in a heatexchanger that heats the metal slurry.

Once the metal-hydride slurry is formed, a pump can pump themetal-hydride slurry from a metal-hydride slurry outlet through a pipeto a metal-hydride slurry storage device, where the chargedmetal-hydride slurry can be stored indefinitely. The chargedmetal-hydride slurry storage device can have an outlet to allow theslurry to be withdrawn by a pump into a slurry carrier (e.g., a tankertruck). The slurry carrier could be anything capable of moving a fluidover a distance, such as automotive vehicles, rail cars, ships, barges,and pipes or other conduits. The carrier could be trucks of the kindthat are used to transport gasoline or fuel oil. The pump can be part ofa service station that is dedicated to serving trucks from a singledistributor or can be available to serve trucks of multipledistributors.

The slurry carrier can transport the charged metal-hydride slurry,including the energy stored in the hydride in the form of hydrogen, froma first location (e.g., a location within a first jurisdiction) to asecond location (e.g., a location within a second jurisdiction). At thesecond location, a station for offloading the transported slurry caninclude a pipe through which a pump can withdraw the slurry from thetransporter and pump it to a charged metal-hydride slurry storage tank.When hydrogen is needed, charged metal-hydride slurry can be pumped bypump from the charged metal-hydride slurry storage tank through a pipeto a slurry inlet and into a discharge device.

A discharge device can contain a heater (e.g., a heating coil) forheating the slurry to a temperature at which the metal hydride of theslurry releases hydrogen. In some cases, the discharge device can heatthe metal-hydride slurry under anhydrous conditions. The heatingtemperature is dependent on the discharge characteristics of the metalhydride in the slurry. For magnesium hydride, the heating temperature isfrom about 250° C. to about 400° C. (e.g., from about 290° C. to about370° C. or from about 320° C. to about 360° C.). Other hydrides can havedifferent temperatures at which they release hydrogen. Generally, thetemperature will be least about 150° C. (e.g., at least about 80° C., atleast about 100° C., at least about 125° C., at least about 175° C., atleast about 200° C., at least about 225° C., at least about 250° C., atleast about 275° C., at least about 300° C., at least about 325° C., atleast about 350° C., at least about 375° C., or at least about 390° C.)and/or at most about 40° C. (e.g., at most about 390° C., at most about375° C., at most about 350° C., at most about 325° C., at most about300° C., at most about 275° C., at most about 250° C., at most about225° C., at most about 200° C., or at most about 175° C.). In somecases, the discharge device can include a catalyst on one or moresurfaces of the discharge device and/or on a stirrer to catalyze thedehydrating process.

The discharge device can operate at a pressure determined by thedischarge characteristics of the metal hydride and the system economics.For magnesium hydride, the highest discharge rates can occur with apressure near atmospheric pressure or lower. In some cases, the hydrogencan be provided at a pressure ranging from 30 psia to 200 psia. In somecase, the hydrogen can be provided at a pressure ranging from 65 psia to120 psia.

The discharge device can be designed to exclude air and water,specifically oxygen and water. The charging device is also designed toexclude air and water as these materials can react with the metalhydride and prevent it from absorbing or desorbing hydrogen.Accordingly, in some cases, the discharge device can be operated underanhydrous conditions.

As the charged metal-hydride slurry is heated and the hydrogen gas isdischarged, the slurry becomes a depleted metal-hydride slurry (ametal-hydride slurry that includes less than a significant amount ofhydrogen, for example, because some of the hydrogen has evolved from theslurry or because the slurry has been newly formed and has not beenhydrided). The depleted reversible slurry can be withdrawn by a pumpthrough a gas outlet into a slurry carrier (which could be, for example,the same trucks used to carry the charged metal-hydride slurry) fortransport back to the first location (or another recharging facility)for recharging. In some cases, a depleted metal-hydride slurry can bemixed with virgin metal and liquid carrier to make a metal slurry.

The hydrogen gas that is discharged from the charged metal-hydrideslurry can be vented through a gas outlet and collected, e.g., bottledin a hydrogen bottle, or directly used. Bottled hydrogen could be used,for example, to power fuel cells in a vehicle. In some cases, thehydrogen can be put to a use other than as an energy source. Forexample, the hydrogen can be used in laboratory work as a carrier gasfor a gas chromatograph, as a reactant in a chemical reaction requiringhydrogen, or as a welding gas, e.g., to replace acetylene. In somecases, the metal-hydride slurry can be used as an energy source for avehicle directly, rather than as a source for bottled hydrogen. Forexample, the charged metal-hydride slurry can be pumped directly into avehicle, e.g., into a storage tank in a vehicle. The vehicle can have adischarge device located within the vehicle, allowing for the evolutionof hydrogen for use as a fuel source in the vehicle. In some cases, thevehicle could also have a charging device, such that the depleted orpartially depleted metal-hydride slurry can be recharged within thevehicle itself.

The charged metal-hydride slurry can be safely stored and transported,and the hydrogen can be easily extracted for use as a fuel. The chargedmetal-hydride slurry can be combustion resistant and can be safelyhandled, stored, and transported. The charged metal-hydride slurry canbe stable at normal environmental temperatures and pressures, forexample, such that hydrogen does not dissociate from the hydride andevolve. The charged metal-hydride slurry can easily be pumped throughconduits and into storage tanks, transportation devices, and/or chargingand discharging devices.

The reaction direction is determined by the pressure of the hydrogen gasand/or the temperature of the reaction. In some examples in whichmagnesium metal is used in the metal slurry and converted into magnesiumhydride, a temperature of from about 250° C. to about 400° C. (e.g.,from about 280° C. to about 350° C. or from about 290° C. to about 320°C.) is required for the hydriding of the magnesium, while a temperatureof from about 280° C. to about 400° C. (e.g., from about 300° C. toabout 380° C., or from about 320° C. to about 360° C.) results indehydriding of the magnesium hydride. Other metal/metal hydride systemscan operate with significantly reduced temperatures and pressures, e.g.,absorption and desorption temperatures of no more than about 250° C.(e.g., no more than about 225° C., no more than about 200° C., no morethan about 175° C., no more than about 150° C., no more than about 125°C., no more than about 100° C., or no more than about 80° C.). In somecases, alloys and/or mixtures of hydrides may improve both the kineticsand the temperature ranges of use. Generally, for the hydriding of themetal, an increase in the hydrogen pressure results in a fasterhydriding reaction and/or a lower temperature requirement for hydriding.In some cases, the hydrogen pressure is at least about 15 psia (e.g., atleast about 50 psia, at least about 100 psia, at least about 150 psia,at least about 200 psia, or at least about 250 psia) and/or at mostabout 300 psia (e.g., at most about 250 psia, at most about 200 psia, atmost about 150 psia, at most about 100 psia, or at most about 50 psia).The pressure will generally be partially dependent upon the temperature(and vice-versa). For example, while magnesium slurries produce arelatively rapid absorption of hydrogen at 300° C. at a pressure of 150psia, a lower temperature might provide a faster reaction.

Generally, a fast reaction is desirable to reduce costs. Duringhydriding, however, heat is produced and must be removed from thesystem. High rates of heat release could potentially decompose theliquid carrier (e.g., mineral oil) in the slurry. In some cases, acombination of temperature and pressure parameters can be used tocontrol the direction and speed of the reaction, and thus the heatproduced. For example, the pressure can be initially relatively low, andcan then be increased as the process proceeds.

As the hydride reaction is reversible, a metal-hydride slurry providedherein can function to transport energy in the form of hydrogenrepeatedly, being charged and discharged many times (e.g., at leastabout 5 times, at least about 10 times, at least about 20 times, atleast about 25 times, at least about 50 times, at least about 75 times,at least about 100 times, at least about 125 times, at least about 150times, at least about 250 times, at least about 500 times, at leastabout 1000 times, or at least about 2000 times). Generally, the greaterthe number of charge/discharge cycles, the more cost-effective thesystem.

The metal-hydride slurries can have a liquid-like flow characteristicthat can allow for the use of existing liquid fuel infrastructure in thestorage and transportation of the slurry. The nature of the carrierliquid, the amount of the dispersant, and the size of the hydrideparticles all affect the viscosity of the slurry. The oil in the slurrycan protect the metal hydride from unintentional contact with moisturein the air. The slurry can serve as a path for the dissipation of heatgenerated from the exothermic charging reaction. The dispersantmaintains the hydride particles in suspension. The dispersant attachesto the particles and fends off adjacent particles to preventagglomeration of the particles. The slurry burns only if high heat isapplied, as by a blow torch, and maintained. Upon removal of heat, theburning of the slurry ceases and flames die out.

The metal-hydride slurries provided herein can be capable of holdingbetween about 3% and about 6% by weight of hydrogen. The slurry in somecase can release from about 70% to about 98% of the uptaken hydrogen(e.g., from about 80 to 98% or from 90 to 98% of the uptaken hydrogen).The residual hydride that remains can then function as a catalyst forthe recharging of the depleted metal-hydride slurry.

Generally, the discharge device is similar to the charging device. Thedischarge device generally includes a fluid-holding vessel and a heatingdevice (e.g., heating coils, a heat exchanger, and/or a heating plug)for heating the slurry therein to the discharging temperature. Wheremagnesium hydride is utilized, the discharging temperature can be atleast about 280° C. (e.g., at least about 300° C., at least about 320°C., at least 340° C., at least about 350° C., at least about 360° C., atleast about 370° C., at least about 380° C., or at least about 390° C.)and/or at most about 400° C. (e.g., at most about 390° C., at most about380° C., at most about 370° C., at most about 360° C., at most about350° C., at most about 340° C., at most about 320° C., or at most about300° C.). Other hydrides can operate with reduced temperatures andpressures. The device further includes a hydrogen gas outlet forreleasing hydrogen gas from the vessel. The discharge device optionallyfurther includes a heat removal apparatus (e.g., a heat pump, heatexchanger, or an insulated counter flow heat exchanger) for reducing thetemperature of the slurry once it is depleted of releasable hydrogen.

In some examples, the discharge device operates on a batch-by-batchbasis. Charged metal-hydride slurry is pumped into the device andheated, at which time hydrogen evolves from the slurry. The depletedslurry is then optionally cooled and pumped from the device (e.g., to astorage tank). The process is then repeated.

In some cases, charged metal-hydride slurry is continuously pumped intothe discharge device, heated, depleted, cooled and removed. FIG. 3illustrates an example of a continuous-mode discharge device 200, inwhich charged metal-hydride slurry 202 is fed by a pump 204 into a firstsection of tubing 206, where it is heated to the desorption temperatureusing heating coils 208. Once heated, the charged metal-hydride slurry202 passes into a desorption chamber 210 having a headspace 211 above asurface 203 of the slurry 202. Hydrogen gas 212 desorbs from the chargedmetal-hydride slurry 202 into the headspace 211, from which it is ventedvia gas outlets 212. A pressure valve 214 can be used to control thepressure within headspace 211. The length of the desorption chamber 210tubing is sufficient, when taken in combination with the flow rate ofthe slurry, to permit substantially all of the available hydrogen todesorb. The slurry, which is now a depleted metal-hydride slurry 216,exits the desorption chamber 210 and enters a third section of tubing220, in which it is cooled to about room temperature, optionally bymeans of a heat exchanger 222 which takes the heat from the depletedmetal-hydride slurry 216 and applies it to the charged metal-hydrideslurry 202 entering the discharge device 200. The depleted metal-hydrideslurry 216 is then pumped out of the discharge device 200, e.g., forstorage and/or transport.

The pressure valve 214 can in some cases be coupled to a cooling system226 to cool the hydrogen gas 212 and to condense any oils 228 which hadvolatilized and vented along with the hydrogen gas 212. The pressurevalve can be located down stream of the oil condenser. The oil willcondense at higher temperatures when under pressure. Any oil 228 socondensed could be added back into the depleted metal-hydride slurry216. The hydrogen gas 212 can in some cases be run through a filter 230,e.g., a charcoal filter, to remove any remaining oils or otherimpurities. The now purified hydrogen gas 212′ can then be fed tofurther processing, such as, for example, bottling. Alternatively, thehydrogen gas 212′ can be supplied to a hydrogen-consuming process suchas a fuel cell or a welding system.

Generally, a first energy source is used to form or extract the hydrogenthat is stored in the hydride slurry. The first energy source is incertain examples an energy source that is readily available at aparticular location (e.g., a first location) and/or is not readilyavailable at, and/or not readily transferable to, a second location.Such energy sources include renewable energy sources such as, e.g.,wind, geothermal, hydroelectric, ocean power (e.g., drawing on theenergy of ocean waves, tides, or on the thermal energy stored in theocean), biomass, and solar energy in the form of heat or electricity.Such energy sources generally do not produce greenhouse gases and arenot subject to depletion. Biomass can produce greenhouse gases, buttypically does not contribute substantial amounts of additionalgreenhouse gases to the atmosphere, since the biomass uses thegreenhouse gases to make itself. In some embodiments, nuclear energy canbe utilized to produce hydrogen. In other embodiments, fuels generallyutilized as energy sources (e.g., coal, oil, and/or natural gas) can beutilized to produce hydrogen. The hydrogen can be produced at a smallnumber of locations, where care can be taken to reduce pollutionresulting from the burning of such fuels.

Many of these energy sources are not themselves easily transportable inan unused and/or stable form, in contrast to fossil fuels. In addition,many of these energy sources are in locations in which the energy demandis low (e.g., areas of low population density and/or littleindustrialization). In some locations, the available energy is greaterthan the energy demand. This excess energy can be stored and transportedto locations of higher energy demand.

While embodiments described above refer generally to forming hydrogen ator near the site of metal hydride formation or charging, hydrogen canitself be stored and transported to metal hydride charging sites. Forinstance, hydrogen can be transported from large scale steam methanereformers to remote markets (e.g., markets several hundred miles away).Other embodiments are within the scope of the following claims.

What is claimed is:
 1. A method for making a metal-hydride slurry, comprising: (a) adding metal or a metal alloy to a liquid carrier to create a metal slurry; and (b) hydriding the metal in the metal slurry to create a metal-hydride slurry.
 2. The method of claim 1, wherein in the metal or metal alloy is in the form of particles in the metal slurry.
 3. The method of claim 2, wherein the particles have a diameter of between 1 micron and 100 microns.
 4. The method of claim 1, further comprising crushing the metal or metal alloy to produce metal particles prior to hydriding the metal.
 5. The method of claim 4, wherein the metal or metal alloy is crushed prior to adding the metal to the liquid carrier.
 6. The method of claim 4, wherein the metal or metal alloy is crushed in the presence of the oil.
 7. The method of claim 1, further comprising melting the metal and spraying the melted metal to produce metal particles prior to hydriding the metal.
 8. The method of claim 7, wherein the melted metal is sprayed into the liquid carrier to produce the metal slurry.
 9. The method of claim 1, wherein the liquid carrier is in the form of a mixture including liquid carrier and magnesium hydride prior to adding the metal or metal alloy to the liquid carrier.
 10. The method of claim 1, wherein the metal slurry comprises at least 1.2 weight percent of metal hydride.
 11. The method of claim 1, further comprising adding metal hydride to the liquid carrier prior to hydriding the metal.
 12. The method of claim 11, wherein the metal hydride is in a metal-hydride slurry and the metal-hydride slurry is added to the liquid carrier prior to hydriding the metal of the metal slurry.
 13. The method of claim 12, wherein the metal is added to the liquid carrier to form a first slurry, wherein the first slurry is mixed with a metal-hydride slurry in a ratio of at least 2:1 to form the metal slurry comprising the metal, a metal hydride, and liquid carrier.
 14. The method of claim 1, wherein the liquid carrier is a mineral oil.
 15. The method of claim 13, wherein the liquid carrier is a light mineral oil.
 16. The method of claim 1, wherein the metal slurry comprises a dispersant.
 17. The method of claim 16, wherein the dispersant is selected from the group consisting of triglyceride, polyacrylic acid, oleic acid, and combinations thereof.
 18. The method of claim 1, wherein the metal is magnesium and the metal hydride is magnesium hydride.
 19. The method of claim 1, wherein the metal is an alloy of magnesium.
 20. The method of claim 19, wherein the metal comprises at least 50 weight percent magnesium and one or more elements selected from the group consisting of vanadium, nickel, and iron. 